Prediction of spectroscopic constants for diatomic molecules in the ground and excited states using time-dependent density functional theory

Copyright 2005 Wiley Periodicals, Inc.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 27(2006), 2 vom: 30. Jan., Seite 163-73
1. Verfasser: Falzon, Chantal T (VerfasserIn)
Weitere Verfasser: Chong, Delano P, Wang, Feng
Format: Aufsatz
Sprache:English
Veröffentlicht: 2006
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Phosphorus 27YLU75U4W Carbon Monoxide 7U1EE4V452 Nitrogen N762921K75 Fluorides Q80VPU408O mehr... Scandium YUJ4U1EW7R
Beschreibung
Zusammenfassung:Copyright 2005 Wiley Periodicals, Inc.
Spectroscopic constants of the ground and next seven low-lying excited states of diatomic molecules CO, N2, P2, and ScF were computed using the density functional theory SAOP/ATZP model, in conjunction with time-dependent density functional theory (TD-DFT) and a recently developed Slater type basis set, ATZP. Spectroscopic constants, including the equilibrium distances r(e), harmonic vibrational frequency omega(e), vibrational anharmonicity omega(e)x(e), rotational constant B(e), centrifugal distortion constant D(e), the vibration-rotation interaction constant alpha(e), and the vibrational zero-point energy E(n)0 were generated in an effort to establish a reliable database for electron spectroscopy. By comparison with experimental values and a similar model with an established larger Slater-type basis set, et-QZ3P-xD, it was found that this model provides reliably accurate results at reduced computational costs, for both the ground and excited states of the molecules. The over all errors of all eight lowest lying electronic states of the molecules under study using the effective basis set are r(e)(+/-4%), omega(e)(+/-5% mostly without exceeding +/-20%), omega(e)x(e)(+/-5% mostly without exceeding 20%, much more accurate than a previous study on this constant of +/-30%), B(e)(+/-8%), D(e)(+/-10%), alpha(e)(+/-10%), and E(n)0(+/-10%). The accuracy obtained using the ATZP basis set is very competitive to the larger et-QZ3P-xD basis set in particular in the ground electronic states. The overall errors in r(e), omega(e)x(e), and alpha(e) in the ground states were given by +/-0.7, +/-10.1, and +/-8.4%, respectively, using the efficient ATZP basis set, which is competitive to the errors of +/-0.5, +/-9.2, and +/-9.1%, respectively for those constants using the larger et-QZ3P-xD basis set. The latter basis set, however, needs approximately four times of the CPU time on the National Supercomputing Facilities (Australia). Due to the efficiency of the model (TD-DFT, SAOP and ATZP), it will be readily applied to study larger molecular systems
Beschreibung:Date Completed 19.04.2006
Date Revised 21.11.2013
published: Print
Citation Status MEDLINE
ISSN:1096-987X